Resin composition for direct vapor deposition, molded articles made by using the same, and surface-metallized lamp housing

ABSTRACT

The direct vapor depositing resin composition of the present invention comprises at least one selected from the group consisting of (A-I): a graft copolymer obtained by graft-polymerizing one or more monomers or a monomer mixture to a complex rubber-like polymer (G) composed of a polyorganosiloxane and a (meth)acrylate-based polymer and (A-II): a graft copolymer obtained by graft-polymerizing one or more monomers or a monomer mixture including an alkyl(meth)acrylate as an essential component to a rubber-like polymer (R) in which the content of diene units is 30% by weight or less in 100% by weight of the whole rubber-like polymer. The direct vapor depositing resin composition of the present invention can provide a beautiful bright appearance after direct vapor deposition of a metal, further, has high level mechanical strengths such as impact strength and the like, and weather resistance, and is also excellent in hot plate welding property with a transparent resin such as PMMA resins, PC resins and the like.

TECHNICAL FIELD

[0001] The present invention relates to a so-called directvapor-depositing resin composition capable of directly forming a layermade of a metal such as aluminum, chromium and the like by metallizingtreatment such as a vacuum vapor depositing method, sputtering methodand the like without imparting surface treatment and under coat, forobtaining a brightening-treated molded article, further, to a resincomposition suitable for lamp housings and, a molded article and lamphousing using the same.

BACKGROUND ART

[0002] Thermoplastic resin molded articles for automobile parts andvarious electric appliance housings are sometimes subjected tometallizing treatment such as formation of a metal layer of copper,chromium, nickel and the like on the surface of a molded article byplating surface treatment, and formation of a metal layer of aluminum,chromium and the like on the surface of a molded article by a vacuumvapor depositing method, sputtering method and the like, for enhancingdesign and other functions.

[0003] Conventionally, in performing surface metallizing treatment by avacuum vapor depositing method, sputtering method and the like on such aresin molded article, it is necessary to form an undercoat-treated layerby painting and plasma polymerization treatment, then, to form a metallayer (thickness: decades to several hundred nm) by a vacuum vapordepositing method and the like, for deleting irregularity on the surfaceof a molded article to obtain smoothness. Usually, thereafter, a topcoat layer made of a silicon-based material and the like is formed forthe purpose of protecting the metal layer. Thus, the metallizingtreatment of a thermoplastic resin molded article requires complicatedmany processes and special apparatuses and expensive treating agents.However, there is conducted, recently, a so-called “direct vapordepositing method” in which a pre-treatment process of forming anundercoat-treated layer is abbreviated.

[0004] However, the design of a bright molded article obtained by this“direct vapor depositing method” varies significantly depending on thekind of a resin material and the surface condition of a resin moldedarticle. In the direct vapor depositing method, particularly, obtainingbeautiful bright appearance without surface hazing is one of importantsubjects.

[0005] For such a field, for example, Japanese Patent ApplicationLaid-Open (JP-A) No. 2001-2869 discloses a thermoplastic resincomposition excellent in direct vapor depositing property comprising arubber-containing graft copolymer obtained by graft-polymerizing avinyl-based monomer (styrene, acrylonitrile) to a rubber-like polymerhaving specific particle size distribution (polyorganosiloxane-basedpolymers, acrylate polymers and the like), and a hard copolymer obtainedby copolymerizing an aromatic vinyl-based monomer, a vinyl cyanide-basedmonomer and optionally other copolymerizable unsaturated monomers.

[0006] Also, JP-A No. 2002-133916 discloses, as a lamp housing materialfor automobile lamp equipments, a rubber-reinforced styrene-based resincomposed of a graft polymer obtained by polymerizing an aromaticvinyl-based monomer (styrene, α-methylstyrene and the like) and a vinylcyanide monomer (acrylonitrile and the like) in the presence of arubber-like polymer having specific particle size distribution(polybutadiene-based rubber, ethylene-propylene-based rubber, acrylicrubber, silicone-based rubber and the like), or composed of a copolymerobtained by polymerizing the above-mentioned graft polymer and theabove-mentioned monomer.

[0007] Automobile tail lamps, stop lamps, head lamps and the like aregenerally constituted of a lens made of a transparent resin such as PMMA(polymethyl methacrylate) resins, PC (polycarbonate) resins and thelike, and a housing supporting the lens. Since such an automobile lamphousing is often exposed to sunlight outdoors, materials excellent inweather resistance are desired, in recent years.

[0008] Further, a so-called hot plate welding method is becominggeneral, in which in connecting a lens made of a transparent resin and ahousing, a heated hot plate is pushed for several seconds to an adhesionpart at which both materials are connected to heat-melt the bothmaterials, and the hot plate is quickly removed, connecting the bothmaterials. In the hot plate welding method, a phenomenon sometimesoccurs in which each part of the both materials adheres to a hot plateof high temperature and stringiness occurs in removing the hot plate,therefore, it is important that this stringiness is scarce in usingthese materials.

[0009] As a material in such a field, for example, JP-A No. 10-310676discloses, a hot plate welding thermoplastic resin composition composedof 10 to 100 parts by weight of a graft polymer obtained bygraft-polymerizing at least one monomer unit selected from the groupconsisting of a vinyl cyanide monomer, an aromatic monomer, a(meth)acrylate monomer and other vinyl monomers in the presence of atleast one rubber-like polymer selected from the group consisting ofcross-linked acrylic rubbers and polyorganosiloxane-based rubbers, and 0to 90 parts by weight of a copolymer composed of an aromatic vinyl-basedmonomer unit, a vinyl cyanide monomer unit and other vinyl-based monomerunits.

[0010] JP-A No. 2000-336235 discloses, as a resin compositionsignificantly improving stringiness in a hot plate welding method, anautomobile lamp equipment lamp body resin prepared by compounding 3 to30% by weight of a homopolymer of a methacrylate or a copolymer ofmonomer components containing a methacrylate as a main component in 97to 70% by weight of a rubber-reinforced styrene-based resin.

[0011] Further, JP-A No. 2000-302824 discloses a thermoplastic resincomposition containing a graft copolymer (A) having a rubber-like graftcopolymer obtained by polymerizing 10 to 1000 parts by weight of (II) amonomer mixture composed of 50 to 100% by weight of a monomer unitcomposed of methyl methacrylate and/or styrene and 0 to 50% by weight ofa monomer unit copolymerizable with the above-mentioned monomer unit, to100 parts by weight of (I) a rubber-like copolymer obtained bypolymerizing a monomer mixture containing an alkyl acrylate monomer unitand a 1,3-butadiene monomer unit, as a thermoplastic resin compositionperforming excellent welding with a PMMA resin, PC resin and the like byvibration welding, showing excellent appearance of melted portionsoccurring in vibration welding and manifesting a good vibration weldingproperty, and a molded body made of this thermoplastic resincomposition.

[0012] However, the resin compositions excellent in a direct vapordeposition property disclosed in JP-A Nos. 2001-2869 and 2002-133916 arenot necessarily sufficient for responding a recent high requirementlevel for brightness. Furthermore, in applications such as an automobilelamp housing and the like, it is necessary that a molded articleadditionally has high weather resistance level. By further reducing theamount of the rubber component having large particle size specificallysuggested in JP-A No. 2001-2869, brightness of higher level can bemanifested, however, in this case, decrease in impact resistance andweather resistance is often remarkable, and it is difficult tosimultaneously satisfy brightness by direct vapor deposition treatment,impact resistance and weather resistance. Also, a hot plate weldingproperty is often not satisfactory.

[0013] On the other hand, in the case of formation of a layer made ofmetal such as aluminum, chromium and the like by a direct vapordeposition method, on the resin compositions disclosed in examples ofJP-A Nos. 10-310676 and 2000-336235, sufficient brightness is notnecessarily obtained and, level recently required is not attained insome cases.

[0014] Regarding the thermoplastic resin composition described inexamples of JP-A No. 2000-302824, disclosed is gloss retention after anexposure time of 500 hours in an accelerated exposure weather resistancetest by a sunshine weather meter, however, sufficient weather resistanceis not obtained for exposure of further longer time and level recentlyrequired is not necessarily attained.

SUMMARY OF THE INVENTION

[0015] The object of the present invention is to provide a direct vapordepositing resin composition giving beautiful bright appearance afterdirect vapor deposition, further, having high level impact resistanceand weather resistance, and also excellent in a hot plate weldingproperty with a transparent resin such as PMMA resins, PC resins and thelike (showing little stringiness), and a molded article and a lamphousing obtained by using this resin composition.

[0016] The present invention relates to a direct vapor depositing resincomposition comprising at least one selected from the group consistingof the following graft copolymers (A-I) and (A-II).

[0017] (A-I): A graft copolymer obtained by graft-polymerizing one ormore monomers or a monomer mixture to a complex rubber-like polymer (G)composed of a polyorganosiloxane and a (meth)acrylate-based polymer.

[0018] (A-II): A graft copolymer obtained by graft-polymerizing one ormore monomers or a monomer mixture including an alkyl(meth)acrylate asan essential component to a rubber-like polymer (R) in which the contentof diene units is 30% by weight or less (including 0% by weight) in 100%by weight of the whole rubber-like polymer.

[0019] Further, the present invention relates to the above-mentioneddirect vapor depositing resin composition comprising a vinyl-based(co)polymer (B) having as a constituent unit at least one selected fromthe group consisting of aromatic alkenyl units, vinyl cyanide units andalkyl(meth)acrylates.

[0020] Furthermore, the present invention relates to the above-mentioneddirect vapor depositing resin composition comprising a polycarbonateand/or polyester (C).

[0021] Still further, the present invention relates to a molded articleobtained by molding the above-mentioned direct vapor depositing resincomposition.

[0022] Even further, the present invention relates to theabove-mentioned molded article of which surface has been metallized bydirect vapor deposition.

[0023] Even still further, the present invention relates to a lamphousing obtained by metallization by direct vapor deposition of thesurface of a molded article obtained by molding the above-mentioneddirect vapor depositing resin composition.

BEST MODES FOR CARRYING OUT THE INVENTION

[0024] The direct vapor depositing resin composition of the presentinvention comprises at least one selected from the group consisting ofthe above-mentioned graft copolymers (A-I) and (A-II). If necessary, thedirect vapor depositing resin composition may further contain theabove-mentioned vinyl-based (co)polymer (B), and, may contain apolycarbonate and/or polyester (C).

[0025] In the direct vapor depositing resin composition of the presentinvention, particularly when a polycarbonate and/or polyester (C) is notcontained, the total content of the graft copolymers (A-I) and (A-II) ispreferably from 5 to 100% by weight, more preferably from 5 to 95% byweight based on the total amount of the graft copolymers (A-I) and(A-II) and the vinyl-based (co)polymer (B). Namely, the content of avinyl-based (co)polymer (B) is preferably from 95 to 0% by weight, morepreferably from 95 to 5% by weight based on the total amount of thegraft copolymers (A-I) and (A-II) and the vinyl-based (co)polymer (B).The content of the vinyl-based (co)polymer (B) is more preferably 10% byweight or more and more preferably 90% by weight or less based on thetotal amount of the graft copolymers (A-I) and (A-II) and a vinyl-based(co)polymer (B).

[0026] In the direct vapor depositing resin composition of the presentinvention, it is preferable that the total content of the graftcopolymers (A-I) and (A-II) is from 5 to 80% by weight based on thetotal amount of the graft copolymers (A-I) and (A-II), vinyl-based(co)polymer (B) and polycarbonate and/or polyester (C), the content ofthe vinyl-based (co)polymer (B) is from 75 to 0% by weight based on thetotal amount of the graft copolymers (A-I) and (A-II), vinyl-based(co)polymer (B) and polycarbonate and/or polyester (C), and the contentof the polycarbonate and/or polyester (C) is from 95 to 20% by weightbased on the total amount of the graft copolymers (A-I) and (A-II),vinyl-based (co)polymer (B) and polycarbonate and/or polyester (C).

[0027] Particularly, when a vinyl-based (co)polymer (B) is used, itscontent is preferably 20% by weight or more, particularly 30% by weightor more and preferably 90% by weight or less, particularly 80% by weightor less based on the total amount of the graft copolymers (A-I) and(A-II), vinyl-based (co)polymer (B) and polycarbonate and/or polyester(C).

[0028] When a polycarbonate and/or polyester (C) is used, its content ispreferably 20% by weight or more, particularly 30% by weight or more andpreferably 90% by weight or less, particularly 80% by weight or lessbased on the total amount of the graft copolymers (A-I) and (A-II),vinyl-based (co)polymer (B) and polycarbonate and/or polyester (C).

[0029] By controlling the ratio of a vinyl-based (co)polymer (B) in aresin composition within the above-mentioned range, the rigidity andmolding processability of the resulting resin composition are improved.By controlling the ratio of a polycarbonate and/or polyester (C) in aresin composition within the above-mentioned range, objects ofcompounding such as heat resistance, impact resistance, chemicalresistance and the like and the object of the present invention can beattained simultaneously.

[0030] In the direct vapor depositing resin composition of the presentinvention, other thermoplastic resins described later may be compoundedin an amount within the range in which various abilities intended in thepresent invention are not significantly disturbed.

[0031] The direct vapor depositing resin composition of the presentinvention may contain the above-mentioned graft copolymer (A-I) or(A-II), and may also contain the above-mentioned graft copolymers (A-I)and (A-II) together. The graft copolymer (A-I) is not required to beused singly, and two or more copolymers may be used in admixture. Thegraft copolymer (A-II) is also not required to be used singly, and twoor more copolymers may be used in admixture.

[0032] The direct vapor depositing resin composition of the presentinvention may contain other graft copolymers than the graft copolymers(A-I) and (A-II), and it is preferable that the graft copolymers (A-I)and (A-II) are used in a ratio of 60% by weight or more based on allgraft copolymers. It is further preferable that the graft copolymers(A-I) and (A-II) are used in a ratio of 100% by weight based on allgraft copolymers.

[0033] A molded article made of such a direct vapor depositing resincomposition of the present invention can be subjected to surfacemetallizing treatment by which a metal layer of aluminum, chromium andthe like is formed on the surface of a molded article by a vacuum vapordepositing or sputtering method, without effecting special pre-treatmentsuch as formation of an under coat-treated layer and the like. A brightmolded article obtained by this direct vapor depositing method shows abeautiful bright appearance without surface haze, since the surfacesmoothness of a molded article made of the direct vapor depositing resincomposition of the present invention is excellent.

[0034] The direct vapor depositing resin composition of the presentinvention is excellent both in impact resistance and weather resistance.

[0035] Further, a molded article made of the direct vapor depositingresin composition of the present invention can be bonded to atransparent resin such as a PC resin, PMMA resin and the like by the hotplate welding method. Additionally, a stringing phenomenon scarcelyoccurs in this procedure, the appearance of the bonded part isexcellent, and its bonding strength is also sufficiently high.

[0036] Therefore, the direct vapor depositing resin composition of thepresent invention is suitable for, for example, lamp housings and thelike, and automobile lamps excellent in brightness, appearance, weatherresistance and impact resistance can be produced efficiently accordingto the present invention.

[0037] The present invention will be described in detail below.

[0038] The polyorganosiloxane constituting the graft copolymer (A-I)according to the present invention preferably contains silicon atomshaving three or more siloxane bonds in an amount of 1 mol % or less(including 0 mol %) based on all silicon atoms in polydimethylsiloxane.When this amount is 1 mol % or less, the finally resulted resincomposition is excellent in impact resistance. This amount is furtherpreferably 0.8 mol % or less since then the resulted resin compositionis excellent both in impact resistance and brightness after direct vapordeposition.

[0039] The method of controlling the amount of silicon atoms havingthree or more siloxane bonds is not particularly restricted, and as anexample, it is preferable to decrease the ratio of silicon-basedmonomers used for forming a cross-linked structure such as ethylorthosilicate, tetraethoxysilane and the like in producing apolyorganosiloxane, and it is more preferable to use no silicon-basedmonomers used for forming a cross-linked structure.

[0040] Further, it is preferable, in producing a polyorganosiloxane, touse an organosiloxane containing a vinyl-polymerizable functional group.The amount of organosiloxane units containing a vinyl polymerizablefunctional group in a polyorganosiloxane is preferably 0.3 mol % or moresince then complexation of a polyorganosiloxane with (meth)acrylaterubber progresses sufficiently, a polyorganosiloxane scarcely bleeds outon the surface of the finally resulted resin composition molded article,and brightness after direct vapor deposition of a molded article andclose adherence between a metal and a resin are excellent. It is furtherpreferable that the amount of organosiloxane units containing avinyl-polymerizable functional group in a polyorganosiloxane is 0.5 mol% or more since then the finally obtained resin composition is excellentboth in impact resistance and brightness after direct vapor deposition.

[0041] The amount of organosiloxane units containing avinyl-polymerizable functional group in a polyorganosiloxane ispreferably 3 mol % or less since then the finally obtained resincomposition is excellent in impact resistance. Further, the amount oforganosiloxane units containing a vinyl-polymerizable functional groupin a polyorganosiloxane is further preferably 2 mol % or less,particularly 1 mol % or less since then the finally obtained resincomposition is excellent both in impact resistance and brightness afterdirect vapor deposition.

[0042] As the polyorganosiloxane, particularly, it is preferable to usea polyorganosiloxane composed of 0.3 to 3 mol % of organosiloxane unitscontaining a vinyl-polymerizable functional group and 97 to 99.7 mol %of a dimethylsiloxane unit in which the amount of silicon atoms havingthree or more siloxane bonds is 1 mol % or less (including 0 mol %)based on all silicon atoms in the polyorganosiloxane.

[0043] As the dimethylsiloxane used in producing a polyorganosiloxane,tri- or more-cyclic dimethylsiloxane-based cyclic bodies are listed, andtri to hepta-cyclic bodies are preferable. Specifically listed arehexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane,decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane and thelike. These are used alone or in combination of two or more.

[0044] The organosiloxane containing a vinyl-polymerizable functionalgroup which can be used in production of a polyorganosiloxane contains avinyl-polymerizable functional group and can be bonded todimethylsiloxane via a siloxane bond. In view of reactivity withdimethylsiloxane, it is preferable to use various alkoxysilane compoundscontaining a vinyl-polymerizable functional group. Specifically listedare methacryloyloxysiloxane such asβ-methacryloyloxyethyldimethoxymethylsilane,γ-methacryloyloxypropyldimethoxymethylsilane,γ-methacryloyloxypropylmethoxydimethylsilane,γ-methacryloyloxypropyltrimethoxysilane,γ-methacryloyloxypropylethoxydiethylsilane,γ-methacryloyloxypropyldiethoxymethylsilane,δ-methacryloyloxybutyldiethoxymethylsilane and the like, vinyl siloxanessuch as tetramethyltetravinylcyclotetrasiloxane and the like,p-vinylphenyldimethoxymethylsilane, further, mercaptosiloxanes such asγ-mercaptopropyldimethoxymethylsilane, γ-mercaptopropyltrimethoxysilaneand the like. These organosiloxanes having a vinyl-polymerizablefunctional group can be used alone or in admixture of two or more.

[0045] The size of a polyorganosiloxane is not particularly restricted,and the average particle size is preferably 600 nm or less, particularly200 nm or less for the purpose of enhancing brightness after directvapor deposition of the finally obtained resin composition.

[0046] The method of producing a polyorganosiloxane is not particularlyrestricted, and the following method is mentioned as one example. First,in a mixture composed of dimethylsiloxane and an organosiloxanecontaining a vinyl-polymerizable functional group, an emulsifier andwater are added and emulsified, to obtain latex. Then, this latex isfinely granulated by using a homo-mixer of finely granulating byshearing force generated by high speed rotation, a homogenizer of finelygranulating by injection force generated by a high pressure generator,and the like. Use of a high pressure emulsifying apparatus such as ahomogenizer and the like is preferable since then the distribution ofthe particle size of the polyorganosiloxane latex is small. This latexafter fine granulation is added in an acid aqueous solution containingan acid catalyst, and polymerized under high temperature. Termination ofpolymerization can be conducted by cooling the reaction solution,further, neutralizing the solution with an alkaline substance such assodium hydroxide, potassium hydroxide, sodium carbonate and the like.

[0047] Regarding addition of an acid catalyst, an acid catalyst may bepreviously mixed with a siloxane mixture, emulsifier and water, or anacid aqueous solution of high temperature may be dropped at a constantspeed into latex in which a siloxane mixture has been finely granulated.However, it is preferable that latex in which a siloxane mixture hasbeen finely granulated is dropped at a constant speed into an acidaqueous solution of high temperature, since then the particle size ofthe resulted polyorganosiloxane can be controlled easily.

[0048] The polymerization time is, when an acid catalyst is mixed andgranulated with a siloxane mixture, emulsifier and water beforepolymerization, preferably 2 hours or longer, particularly 4 hours orlonger. In the case of the method in which latex in which a siloxanemixture has been finely granulated is dropped into an aqueous solutionof an acid catalyst, it is preferable to keep the reaction solution forabout 1 hour after completion of addition of the latex.

[0049] The polymerization temperature is preferably 50° C. or more,particularly 80° C. or more. The upper limit of the polymerizationtemperature is not particularly restricted, and usually about 95° C.

[0050] Preferable as the emulsifier used are anionic emulsifiers such assodium alkylbenzensulfonates, sodium polyoxyethylene alkyl phenyl ethersulfates and the like, and of them, sulfonic acid-based emulsifiers suchas sodium alkylbenzenesulfonates, sodium laurylsulfonate and the likeare particularly preferable. These emulsifiers may be used alone or incombination of two or more. The use amount of an emulsifier ispreferably 0.05 parts by weight or more based on 100 parts by weight ofa siloxane mixture since then dispersed conditions is usually stable andemulsified condition of fine particles can be kept, and preferably 5parts by weight or less based on 100 parts by weight of a siloxanemixture since then the color of a molded article is scarcely influencedby the color of an emulsifier itself or by deterioration of a resincomposition ascribable to it.

[0051] Listed as the acid catalyst used in polymerization of apolyorganosiloxane are sulfonic acids such as aliphatic sulfonic acids,aliphatic substituted benzenesulfonic acids, aliphatic substitutednaphthalenesulfonic acids and the like, and mineral acids such assulfuric acid, hydrochloric acid, nitric acid and the like. These acidcatalysts may be used alone or in combination of two or more. As theacid catalyst, aliphatic substituted benzenesulfonic acids arepreferable and n-dodecylbenzenesulfonic acid is particularly preferablebecause of excellent action of stabilizing polyorganosiloxane latex.When n-dodecylbenzenesulfonic acid is combined with a mineral acid suchas sulfuric acid and the like, an influence exerted by the color of anemulsifier used in polyorganosiloxane latex on the color of a resincomposition molded article can be suppressed to lower level. Theaddition amount thereof may be appropriately determined, and usuallyfrom about 0.1 to 20 parts by weight based on 100 parts by weight of asiloxane mixture.

[0052] The (meth)acrylate-based polymer constituting the complexrubber-like polymer (G) used in the graft copolymer (A-I) is obtained bypolymerizing an alkyl (meth)acrylate monomer, or a monomer mixturecontaining one or more alkyl(meth)acrylates. The (meth)acrylate-basedpolymer may contain other monomers than the alkyl (meth)acrylatemonomer.

[0053] Listed as the alkyl(meth)acrylate monomer are, for example, alkylacrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate,n-butyl acrylate, 2-ethylhexyl acrylate and the like, and alkylmethacrylates such as hexyl methacrylate, 2-ethylhexyl methacrylate,n-lauryl methacrylate and the like. Of them, n-butyl acrylate ispreferably used since then the resulted resin composition is excellentin impact resistance. These may be used alone or in combination of twoor more.

[0054] Polymerization can be conducted according to known methods. Asdescribed later, a graft crossing agent or cross-linking agent may beused.

[0055] The method of producing a complex rubber-like polymer (G) used inthe present invention is not particularly restricted, and there arelisted a method in which separate latexes of a polyorganosiloxane and a(meth)acrylate-based polymer are hetero-aggregated or co-thickened, amethod in which, in the presence of any one or more latexes, monomers(including also a mixture) forming other one or more polymers arepolymerized and complexed, and other methods. Of them, a method ispreferable in which (meth)acrylate monomers (including also a mixture)as described above are polymerized in the presence of an organosiloxanein the form of latex since then the resulted resin composition isexcellent in impact resistance and brightness after direct vapordeposition.

[0056] If necessary, it is also possible to use a graft crossing agentand a cross-linking agent in this procedure. Listed as the graftcrossing agent and cross-linking agent which can be used are, forexample, allyl methacrylate, triallyl cyanurate, triallyl isocyanurate,divinylbenzene, ethylene glycol dimethacrylate, propylene glycoldimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycoldimethacrylate and the like. These may be used alone or in combinationof two or more. The addition amount thereof may be appropriatelydetermined, and is preferably from about 0.3 to 6 parts by weight basedon 100 parts by weight of (meth)acrylate monomers (including also amixture) since then the resulted resin composition is excellent inimpact resistance and brightness after direct vapor deposition.

[0057] A monomer mixture constituted of these alkyl(meth) acrylates, andif necessary, a graft crossing agent and a cross-linking agent can beradical-polymerized in bulk, continuously or intermittently to apolyorganosiloxane in the form of latex, to obtain apolyorganosiloxane/(meth)acrylate-based complex rubber-like polymer (G).

[0058] Regarding the ratio of polyorganosiloxane/(meth)acrylate-basedpolymer constituting a complex rubber-like polymer (G), it is preferablethat the content of a polyorganosiloxane in a complex rubber-likepolymer (G) is 1% by weight or more based on the total amount of apolyorganosiloxane and a (meth)acrylate-based polymer (monomer mixture)since then the resulted resin composition is excellent in impactresistance. On the other hand, the content of a polyorganosiloxane in acomplex rubber-like polymer (G) is preferably 99% by weight or less,more preferably 90% by weight or less based on the total amount of apolyorganosiloxane and a (meth)acrylate-based polymer (monomer mixture)since then the resulted resin composition is excellent in balance ofimpact resistance and brightness after direct vapor deposition. When theamount of a polyorganosiloxane in a complex rubber-like polymer (G) isin this range, the resulted resin composition is excellent in impactresistance and brightness after direct vapor deposition. The amount of apolyorganosiloxane in a complex rubber-like polymer (G) is furtherpreferably 2% by weight or more, particularly 3% by weight or more, andfurther preferably 50% by weight or less, particularly 10% by weight orless based on the total amount of a polyorganosiloxane and a(meth)acrylate-based polymer (monomer mixture).

[0059] The average particle size of a complex rubber-like polymer (G) isnot particularly restricted, and preferably less than 400 nm, furtherpreferably 300 nm or less since then the resulted resin composition isexcellent in bright appearance after direct vapor deposition. The lowerlimit of the average particle size of a complex rubber-like polymer (G)is not particularly restricted, and usually about 30 nm.

[0060] It is preferable that the ratio of rubber-like polymers having aparticle size of 500 nm or more is 4% by weight or less (including 0% byweight), particularly 3% by weight or less, further 2% by weight or lessbased on 100% by weight of all rubber-like polymers including a complexrubber-like polymer (G) since then a molded article having a beautifulbright appearance is obtained.

[0061] The graft copolymer (A-I) can be produced byemulsion-graft-polymerizing vinyl-based monomers, preferably, at leastone monomer component selected from the group consisting of aromaticalkenyl compounds, alkyl (meth)acrylates and vinyl cyanide compounds toa complex rubber-like polymer (G) described above.

[0062] Of monomer components, styrene, α-methylstyrene, vinyltoluene andthe like are listed, for example, as the aromatic alkenyl compound. Asthe alkyl(meth)acrylate, for example, methyl methacrylate, ethylmethacrylate, 2-ethylhexyl methacrylate, methyl acrylate, ethylacrylate, butyl acrylate and the like are listed. As the vinyl cyanidecompound, for example, acrylonitrile, methacrylonitrile and the like arelisted. Of them, a mixture of styrene and acrylonitrile is preferablyused as the monomer component since then the resulted resin compositionis excellent in impact resistance. The content of styrene in 100% byweight of this mixture is preferably 10% by weight or more, andpreferably 90% by weight or less. On the other hand, it is preferable touse methyl methacrylate alone or a mixture containing methylmethacrylate in an amount preferably of 50% by weight or more since thenthe resulted resin composition is excellent in brightness after directvapor deposition. These can be appropriately selected depending on theobject.

[0063] Regarding the weight ratio of a complex rubber-like polymer (G)and a vinyl-based monomer used in graft polymerization, inemulsion-graft-polymerization, it is preferable that the content of acomplex rubber-like polymer (G) is 10% by weight or more and the contentof a vinyl-based monomer is 90% by weight or less (in total: 100% byweight, the same in the followings) since then the finally resultedresin composition is excellent in impact resistance and also excellentin brightness after direct vapor deposition. On the other hand,regarding the weight ratio of a complex rubber-like polymer (G) and avinyl-based monomer used in emulsion-graft-polymerization, it ispreferable that the content of a complex rubber-like polymer (G) is 80%by weight or less and the content of a vinyl-based monomer is 20% byweight or more since then the finally resulted resin composition isexcellent in impact resistance. When emulsion-graft-polymerization isconducted at such a weight ratio, the finally resulted resin compositionis excellent in impact resistance, flowability and brightness afterdirect vapor deposition.

[0064] Particularly, regarding the weight ratio of a complex rubber-likepolymer (G) and a vinyl-based monomer used inemulsion-graft-polymerization, it is preferable that the content of acomplex rubber-like polymer (G) is 30% by weight or more and the contentof a vinyl-based monomer is 70% by weight or less, and it is preferablethat the content of a complex rubber-like polymer (G) is 70% by weightor less and the content of a vinyl-based monomer is 30% by weight orless. When emulsion-graft-polymerization is conducted at such a weightratio, the finally resulted resin composition manifests excellent impactresistance and direct vapor deposition appearance excellent inbrightness in good balance.

[0065] The graft copolymer (A-I) can be produced by radicalpolymerization using an emulsifier. In monomer components, various chaintransfer agents for controlling the graft ratio and the molecular weightof graft components, for example, mercaptan-based compounds,terpene-based compounds, α-methylstyrene dimer and the like may beadded. The polymerization conditions are not particularly restricted,and can be appropriately selected depending on necessity.

[0066] As the radical polymerization initiator used in producing a graftcopolymer (A-I) and a (meth)acrylate-based polymer in a complexrubber-like polymer (G) described above, peroxides, azo-basedinitiators, redox type initiators prepared by combining oxidizer andreducing agents, and the like can be used. Of them, redox typeinitiators are preferably used, and particularly, it is preferable touse redox type initiators combining ferrous sulfate . sodiumpyrophosphate . glucose . hydroperoxide or ferrous sulfate . disodiumethylenediamine tetraacetate . rongalite . hydroperoxide.

[0067] The emulsifier used in producing a graft copolymer (A-I) and a(meth)acrylate-based polymer in a complex rubber-like polymer (G)described above is not particularly restricted. Since an emulsifier usedin production of a polyorganosiloxane is contained in a complexrubber-like polymer (G), this may be used itself, and if necessary,other emulsifiers may further be added. As the emulsifier which can beused in this case, it is preferable to use various salts of carboxylicacids such as sodium sarcocinate, fatty potassium, fatty sodium,dipotassium alkenylsuccinate, rosin soap and the like, and anionicemulsifiers such as alkyl sulfates, sodium alkylbenzenesulfonates,sodium polyoxyethylene alkylphenyl ether sulfate and the like since thenthe stability of latex in emulsion-polymerization is excellent andpolymerization ratio is enhanced. These are classified and useddepending on the object. Further, it may also be permissible that theemulsifier used in preparation of a complex rubber-like polymer (G) isused as it is and emulsifiers are not additionally added inemulsion-graft-polymerization.

[0068] The graft copolymer (A-II) used in the present invention isobtained by graft-polymerizing one or more monomers or a monomer mixtureincluding an alkyl (meth)acrylate as an essential component to arubber-like polymer (R) in which the content of diene units is 30% byweight or less (including 0% by weight) in 100% by weight of allrubber-like polymers contained in a resin composition. The graftcopolymer (A-II) may be used singly or in combination of two or more,and can be selected optionally depending on its application.

[0069] The rubber-like polymer (R) which can be used is not particularlyrestricted excepting the above-mentioned conditions, and exemplified arediene-based rubber such as polybutadiene rubber, styrene-butadienerubber, acrylonitrile-butadiene rubber, butyl acrylate-butadiene rubberand the like, acrylic rubber such as butyl acrylate rubber,butadiene-butyl acrylate rubber, 2-ethylhexyl acrylate-butyl acrylaterubber, 2-ethylhexyl methacrylate-butyl acrylate rubber, stearylacrylate-butyl acrylate rubber, dimethylsiloxane-butyl acrylate rubber,silicone/butyl acrylate complex rubber and the like, polyolefin-basedrubber polymers such as ethylene-propylene rubber,ethylene-propylene-diene rubber and the like, silicone-based rubberpolymers such as polydimethylsiloxane rubber and the like. These can beused alone or in combination of two or more. Of course, the diene unitratio is restricted in diene-based rubber.

[0070] In these rubber-like polymers (R), the content of diene units in100% by weight of all rubber-like polymers is 30% by weight or less,preferably 10% by weight or less, further preferably less than 1% byweight since then the resulted resin composition is excellent in weatherresistance.

[0071] It is preferable that the rubber-like polymer (R) contains atleast one monomer of alkyl acrylates having an alkyl group containing 2to 8 carbon atoms, more preferably 4 to 8 carbon atoms such as methylacrylate, ethyl acrylate, n-butyl acrylate, n-propyl acrylate,2-ethylhexyl acrylate and the like, and it is preferable that the ratioof alkyl acrylate units having an alkyl group containing 2 to 8 carbonatoms in the rubber-like polymer (R) is from 70 to 90% by weight sincethen the resulted resin composition is excellent in weather resistance,brightness after direct vapor deposition and the appearance of a hotplate welding connected part.

[0072] Further, in the rubber-like polymer (R), copolymerizablevinyl-based monomers other than the above-mentioned monomers can beintroduced in an amount of 30% by weight or less. Such vinyl-basedmonomers are not particularly restricted, and examples thereof includearomatic vinyl-based monomers such as styrene, α-methylstyrene,vinyltoluene and the like, vinyl cyanide monomers such as acrylonitrile,methacrylonitrile, graft crossing agents and cross-linking agents suchas allyl methacrylate, triallyl cyanurate, triallyl isocyanurate,divinylbenzene, ethylene glycol dimethacrylate, propylene glycoldimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycoldimethacrylate and the like, and other monomers. These may be used aloneor in combination of two or more.

[0073] The graft components of the graft copolymer (A-II) are composedof one or more monomers or a monomer mixture including analkyl(meth)acrylate as an essential component, or one or more monomersor a monomer mixture including an alkyl(meth)acrylate as an essentialcomponent, and other vinyl-based monomers copolymerizable with them.

[0074] Examples of the alkyl(meth)acrylate used includemethyl(meth)acrylate, ethyl(meth)acrylate, n-propyl (meth)acrylate,n-butyl(meth)acrylate, 2-ethylhexyl (meth)acrylate and the like. Thesemay be used alone or in combination of two or more. Of them, it ispreferable to use methyl methacrylate since then the resulted resincomposition is excellent in balance of impact resistance and brightnessafter direct vapor deposition.

[0075] The copolymerizable other vinyl-based monomers are notparticularly restricted, and the above-mentioned aromatic vinyl-basedmonomers, vinyl cyanide-based monomers and the like are listed.

[0076] The content of an alkyl(meth)acrylate in 100% by weight of allgraft components (the above-mentioned one or more monomers or a monomermixture including a alkyl (meth)acrylate as an essential component, tobe graft-polymerized to a rubber-like polymer (R)) is preferably from 20to 100% by weight, more preferably from 50 to 100% by weight, furtherpreferably from 70 to 100% by weight, particularly preferably from 80 to100% by weight since then the resulted resin composition is excellent inweather resistance, and brightness after direct vapor deposition.

[0077] The method of producing a graft copolymer (A-II) is notparticularly restricted, and for example, a graft copolymer (A-II) canbe produced by emulsion-graft-polymerizing one or more monomercomponents (one or more monomers or a monomer mixture) to theabove-mentioned rubber-like polymer (R).

[0078] Regarding the weight ratio of a rubber-like polymer (R) and oneor more monomers or a monomer mixture used in graft polymerization, inemulsion-graft-polymerization, the content of a rubber-like polymer (R)in 100% by weight of a graft copolymer (A-II) is preferably 10% or more,more preferably 30% or more, and preferably 90% by weigh or less, morepreferably 80% by weight or less. When emulsion-graft-polymerization isconduced at such a weight ratio, the finally resulted resin compositionmanifests excellent impact resistance and a direct vapor depositionappearance excellent in brightness, in good balance.

[0079] The graft copolymer (A-II) can be produced byradical-polymerization using an emulsifier. Usually, a rubber-likepolymer (R) is previously produced by emulsion-polymerization, and thenone or more monomers or a monomer mixture as graft components are addedto this rubber-like polymer latex, and they are graft-polymerized toobtain a graft copolymer (A-II). In monomer components, various chaintransfer agents for controlling the graft ratio and the molecular weightof graft components, for example, mercaptan-based compounds,terpene-based compounds, α-methylstyrene dimer and the like may beadded. The polymerization conditions are not particularly restricted,and can be appropriately selected depending on necessity.

[0080] As the radical polymerization initiator used in producing arubber-like polymer (R) and a graft copolymer (A-II), peroxides,azo-based initiators, redox type initiators prepared by combiningoxidizer and reducing agents, and the like can be used. Of them, redoxtype initiators are preferably used, and particularly, it is preferableto use redox type initiators combining ferrous sulfate . sodiumpyrophosphate . glucose . hydroperoxide or ferrous sulfate . disodiumethylenediamine tetraacetate . rongalite . hydroperoxide.

[0081] The emulsifier used in producing a rubber-like polymer (R) and agraft copolymer (A-II) is not particularly restricted, it is preferableto use various salts of carboxylic acids such as sodium sarcocinate,fatty potassium, fatty sodium, dipotassium alkenylsuccinate, rosin soapand the like, and anionic emulsifiers such as alkyl sulfates, sodiumalkylbenzenesulfonates, sodium polyoxyethylene alkylphenyl ether sulfateand the like since then the stability of latex inemulsion-polymerization is excellent and polymerization ratio isenhanced. These are classified and used depending on the object.Further, it may also be permissible that the emulsifier used inpreparation of a rubber-like polymer (R) is used as it is andemulsifiers are not additionally added in emulsion-graft-polymerization.

[0082] The latex of graft copolymers (A) obtained byemulsion-graft-polymerization [graft copolymers (A-I) and (A-II)] can berecovered as a graft copolymer (A) by, for example, a wet method inwhich it is added into hot water containing a dissolved coagulant tocause coagulation in the form of slurry, a spray dry method in which agraft copolymer (A) latex is sprayed into a heated atmosphere to recovera graft copolymer (A) semi-directly, and the other methods.

[0083] As the coagulant used in the wet recovering method, inorganicacids such as sulfuric acid, hydrochloric acid, phosphoric acid, nitricacid and the like, and metal salts such as potassium chloride, calciumacetate, aluminum sulfate, alum and the like, can be used. The coagulantused is selected in a pair with an emulsifier used in polymerization.Namely, when carboxylic acid soaps such as fatty soaps and rosin soapand the like are only used as the emulsifier, a graft copolymer (A) canbe recovered using any coagulant, however, when an emulsifier showingstable emulsification power also in an acid region such as a sodiumalkylbenzenesulfonate is contained, the above-mentioned inorganic acidsare insufficient, and it is necessary to use a metal salt as acoagulant.

[0084] For obtaining a graft copolymer (A) in dry condition from a graftcopolymer (A) in the form of slurry obtained by the wet recoveringmethod, after a process such as a method in which first, a remainingemulsifier residue is eluted in water and washed, then, this slurry isdehydrated by centrifugation, press dehydrator and the like, then, driedby an air flow drier and the like or a method in which dehydration anddrying are conducted simultaneously by a squeezing dehydrator, extruderand the like, a dried graft copolymer (A) can be obtained in the form ofpowder or granule. Further, in this procedure, it is also possible thatwhich discharged from a squeezing dehydrator or extruder is carrierdirectly to an extruder or a molding machine for producing a resincomposition, to give a molded article.

[0085] The vinyl-based (co)polymer (B) which can be used in the resincomposition of the present invention is a (co)polymer having as aconstituent unit at least one selected from the group consisting ofaromatic alkenyl units, vinyl cyanide units and alkyl(meth)acrylateunits, namely, is a (co)polymer obtained by polymerizing monomers (alsoincluding a mixture) including any one or more of aromatic alkenylcompounds, vinyl cyanide compounds and alkyl(meth)acrylate compounds. Byinclusion of the vinyl-based (co)polymer (B), other effects than theobject of the present invention such as improvement in moldingprocessability of the resulted resin composition, impartment of heatresistance, and the like can be obtained, and can be selected dependingon its object.

[0086] Further, the vinyl-based (co)polymer (B) may be a copolymerobtained by polymerizing a monomer mixture containing monomers otherthan aromatic alkenyl compounds, vinyl cyanide compounds andalkyl(meth)acrylate compounds, and for example, it is also preferablethat the vinyl-based (co)polymer (B) is a copolymer obtained bypolymerizing a monomer mixture composed of an aromatic alkenyl compound,vinyl cyanide compound and N-substituted maleimide.

[0087] As the aromatic alkenyl units, vinyl cyanide units andalkyl(meth)acrylate units constituting them, the same compounds as thoseused in the above-mentioned graft polymerization can be used.

[0088] As the other monomer components than these compounds,maleimide-based monomers, maleic anhydride and the like are listed. Asthe maleimide-based monomer, for example, maleimide, N-methylmaleimide,N-ethylmaleimide, N-phenylmelaimide, N-propylmaleimide,N-cyclohexylmaleimide and the like are listed.

[0089] As the vinyl-based (co)polymer (B), resins such as anacrylonitrile-styrene copolymer (SAN) resin, polymethyl methacrylate(PMMA) resin, styrene-methyl methacrylate copolymer (MS) resin,acrylonitrile-α methylstyrene copolymer (αSAN) resin,styrene-acrylonitrile-N-phenylmaleimide ternary copolymer (SAM) resin,polystyrene resin, acrylonitrile-styrene-methyl methacrylate ternarycopolymer and the like are specifically preferable. The vinyl-based(co)polymer (B) may be used alone or in combination of two or more.

[0090] A vinyl-based (co)polymer (B) having any molecular weight can beused.

[0091] The polycarbonate (C) which can be used in the resin compositionof the present invention is composed of a dihydroxydiarylalkane, and maybe branched optionally. By inclusion of the polycarbonate (C), the heatresistance and impact resistance of the resulted resin composition canbe improved.

[0092] The dihydroxyarylalkane may have an alkyl group, chlorine atom orbromine atom at the ortho position to a hydroxyl group. Preferable asthe dihydroxyarylalkane are 4,4′-dihydroxy-2,2′-diphenylpropane(bisphenol A), tetramethyl bisphenol A,bis(4-hydroxyphenyl)-p-diisopropylbenzene and the like.

[0093] As the polycarbonate (C), those having any molecular weight canbe used.

[0094] The polycarbonate (C) can be produced by a known method, and ingeneral, produced by reacting a dihydroxy compound or a polyhydroxycompound with a phosgene or a diester of carbonic acid.

[0095] A branched polycarbonate is produced by substituting a part of adihydroxy compound, for example, 0.2 to 2 mol % of this with apolyhydroxy compound. As the polyhydroxy compound, there are listed1,4-bis(4′,4,2-dihydroxytriphenylmethyl)-benzene, phloroglucinol,4,6-dimethyl-2,4,6-tri(4-hydroxyphenyl)-heptene-2,4,6-dimethyl-2,4,6-tri(4-hydroxyphenyl)heptane,1,3,5-tri(4-hydroxyphenyl)-benzene, 1,1,1-tri(4-hydroxyphenyl)-ethane,2,2-bis[4,4′-(4,4′-dihydroxyphenyl)cyclohexyl]propane and the like.

[0096] The polycarbonate (C) may be used alone or in combination of twoor more.

[0097] The polyester (C) which can be used in the resin composition ofthe present invention is mainly composed of a polyalkyleneterephthalate, and preferably contains, in a ratio of 50% by weight ormore, that composed of an aromatic dicarboxylic acid having 8 to 22carbon atoms and an alkylene glycol or cycloalkylene glycol having 2 to22 carbon atoms. By inclusion of the polyester (C), the moldingprocessability and chemical resistance of the resulted resin compositioncan be improved.

[0098] The polyester (C) may also contain, if necessary, an aliphaticdicarboxylic acid, for example, adipic acid, sebacic acid and the like,as a constituent unit, in an amount preferably of 80% by weight or less.Also, the polyester (C) may contain a polyalkylene glycol such aspolyethylene glycol and the like as a constituent unit.

[0099] As the polyester (C) used, polyethylene terephthalate,polytetramethylene terephthalate and the like are particularlypreferable.

[0100] As the polyester (C), those having any molecular weight can beused.

[0101] The polyester (C) may be used alone or in combination of two ormore.

[0102] When these polycarbonates and polyesters are used, each of themmay be used singly, or they may be used in any ratio, if necessary.

[0103] In the direct vapor depositing resin composition of the presentinvention, other thermoplastic resins may be compounded in an amountwithin the range in which various abilities intended in the presentinvention are not significantly disturbed, if necessary.

[0104] The other thermoplastic resin is not particularly restricted, andexamples thereof include polyolefins such as polyvinyl chloride,polyethylene, polypropylene and the like, styrene-based elastomers suchas styrene-butadiene-styrene (SBS), styrene-butadiene (SBR),hydrogenated SBS, styrene-isoprene-styrene (SIS) and the like, variousolefin-based elastomers, various polyester-based elastomers, polyacetalresins, modified polyphenylene ethers (modified PPE resins),ethylene-vinyl acetate copolymer, PPS resin, PES resin, PEEK resin,polyallylate, liquid crystal polyester resins, polyamide resins (nylon)and the like, and ABS resins, ASA resins andstyrene-acrylonitrile-silicone (SAS) resin and the like out of the rangeof the present invention. These other thermoplastic resins may be usedalone or in combination of two or more.

[0105] The use amount of these other thermoplastic resins is preferably80 parts by weight or less in 100 parts by weight of a resincomposition.

[0106] The resin composition of the present invention can be produced bymixing and dispersing a graft copolymer (A), if necessary, a vinyl-based(co)polymer (B), polycarbonate and/or polyester (C), other thermoplasticresin by a V shaped blender or Henschel mixer and the like, and meltkneading this mixture by using an extruder or a kneader such as aBanbury mixer, press kneader, roll and the like.

[0107] The resulted direct vapor depositing resin composition of thepresent invention can be used itself, or if necessary, after compoundingof additives such as dyes, pigments, heat stabilizers, weather resistantaids, reinforcing agents, fillers, flame retardants, flame retardantaids, foaming agents, lubricants, plasticizers, antistatic additives andthe like, as a production raw material of a molded article. The resincomposition can be made into the intended molded article by variousmolding methods such as an injection molding method, extrusion moldingmethod, blow molding method, compression molding method, calendermolding method, inflation molding method and the like.

[0108] The molded article made of the resin composition of the presentinvention which has been primary-processed by the above-mentionedvarious molding methods can be subjected to surface metallizingtreatment with aluminum, chromium and the like by a vacuum vapordeposition method or sputtering method, without special pre-treatmentsuch as formation of an undercoat-treated layer and the like, asdescribed above. This metallized bright surface may be left as it is,however, for protecting the surface from generation of flaw by dust andthe like, it is also possible to effect top coat treatment of forming acoat made of a silicon-based material and the like by painting and thelike.

[0109] As the industrial application examples of these resincompositions of the present invention, listed are automobile parts,particularly, housings of head lamps and tail lamps, domestic electricparts such as illumination equipment housings and the like, OA equipmenthousings, interior members and the like.

[0110] The direct vapor depositing resin composition of the presentinvention is, particularly, suitable for lamp housings. Abrightening-treated lamp housing molded article obtained by metallizingby direct vapor deposition of the surface of a molded article obtainedby molding the direct vapor depositing resin composition of the presentinvention is made into contact with a resin made of a PC resin, PMMAresin and the like by a method such as hot plate welding, vibrationwelding and the like. The molded article of the present invention isparticularly suitable for hot plate welding since it is excellent instringing property.

EXAMPLES

[0111] The following examples and comparative examples will illustratedthe present invention further specifically, but do not limit the scopeof the invention. % and parts in the following examples and comparativeexamples are by weight unless otherwise stated.

Production Example 1 Production of Polyorganosiloxane (L-1) Latex

[0112] Octamethylcyclotetrasiloxane 98 partsγ-methacryloyloxypropyldimethoxymethylsilane 2 parts were mixed toobtain 100 parts of a siloxane-based mixture. To this was added anaqueous solution composed of sodium dodecylbenzenesulfonate 0.67 partsion exchanged water 300 parts, and the mixture was stirred for 2 minutesby a homomixer at 10000 rotations/min., then, passed through ahomogenizer under a pressure of 20 MPa, to obtain a stable pre-mixedorganosiloxane latex. On the other hand, into a reactor equipped with areagent injection vessel, cooling tube, jacket heater and stirringapparatus was charged dodecylbenzenesulfonic acid 10 parts ion exchangedwater 90 parts, to prepare a 10% dodecylbenzenesulfonic acid aqueoussolution.

[0113] This aqueous solution was heated to 85° C. and under thiscondition, previously mixed organosiloxane latex was dropped over 4hours, and after completion of addition, its temperature was maintainedfor 1 hour, then, cooled to 40° C. or lower. Then, the reaction productwas neutralized with a sodium hydroxide aqueous solution to pH 7,completing polymerization.

[0114] Thus obtained polyorganosiloxane (L-1) latex was dried at 170° C.for 30 minutes, and the solid content was measured to find it was 17.7%.The average particle size of the polyorganosiloxane (L-1) in latex was50 nm, and the ratio of rubber-like polymers having a particle size of500 nm or more was about 0%. The content of organosiloxane units havinga vinyl polymerizable functional group in polydimethylsiloxane was 0.65mol %, and the content of silicon atoms having three or more siloxanebonds was 0 mol % based on all silicon atoms in polydimethylsiloxane.

Production Example 2 Production of Polyorganosiloxane

[0115] Octamethylcyclotetrasiloxane 95.5 partsγ-methacryloyloxypropyldimethoxymethylsilane 0.5 parts tetraethoxysilane4 parts were mixed to obtain 100 parts of a siloxane-based mixture. Tothis was added an aqueous solution composed of dodecylbenzenesulfonicacid 1 part sodium dodecylbenzenesulfonate 1 part ion exchanged water200 parts, and the mixture was stirred for 2 minutes by a homomixer at10000 rotations/min., then, passed through a homogenizer under apressure of 20 MPa, to obtain a stable pre-mixed organosiloxane latex.

[0116] This pre-mixed organosiloxane latex was charged into a reactorequipped with a cooling tube, jacket heater and stirring apparatus, andthe mixture was heated at 80° C. for 5 hours, then, cooled to about 20°C., and left as it was for 48 hours. Then, the reaction product wasneutralized with a sodium hydroxide aqueous solution to pH 7, completingpolymerization.

[0117] Thus obtained polyorganosiloxane (L-2) latex was dried at 170° C.for 30 minutes, and the solid content was measured to find it was 36.5%.The average particle size of the polyorganosiloxane (L-2) in latex was160 nm, and the ratio of rubber-like polymers having a particle size of500 nm or more was 0.3%. The content of organosiloxane units having avinyl polymerizable functional group in polydimethylsiloxane was 0.3 mol%, and the content of silicon atoms having three or more siloxane bondswas 1.5 mol % based on all silicon atoms in polydimethylsiloxane.

Production Example 3 Production of Polyorganosiloxane (L-3) Latex

[0118] Polymerization was conducted in the same manner as in ProductionExample 1 except that the siloxane mixture used was constituted of 96parts of octamethylcyclotetrasiloxane, 2 parts ofγ-methacryloyloxypropyldimethoxymethylsilane, and 2 parts oftetraethoxysilane, and as a result, the solid content was 17.3%, theaverage particle size was 50 nm, the ratio of rubber-like polymershaving a particle size of 500 nm or more was about 0%, the content ofmethacryloxysiloxane units was 0.7 mol %, and the content of siliconatoms having three or more siloxane bonds was 1.2 mol %.

Production Example 4 Production of Polyorganosiloxane/Acrylate ComplexRubber-Based Graft Copolymer (A-I-1)

[0119] Into a reactor equipped with a reagent injection vessel, coolingtube, jacket heater and stirring apparatus was chargedpolyorganosiloxane latex (L-1) produced in 8 parts Production Example 1(solid content) Emal NC-35 (polyoxyethylene alkylphenyl ether 0.2 partssulfate; manufactured by Kao Corp.) ion exchanged water 148.5 parts, andthey were mixed, then, to this was added a mixture composed of n-butylacrylate 42 parts allyl methacrylate 0.3 parts 1,3-butylene glycoldimethacrylate 0.1 part t-butyl hydroperoxide 0.11 parts. The atmospherewas purged with nitrogen by passing a nitrogen flow through thisreactor, the inner temperature was raised to 60° C., and at this point,an aqueous solution composed of ferrous sulfate hepta-hydrate 0.000075parts disodium ethylenediamine tetraacetate 0.000225 parts rongalite 0.2parts ion exchanged water 10 parts was added, to initiate radicalpolymerization. By polymerization of the acrylate component, the liquidtemperature rose to 78° C. This condition was maintained for 1 hour tocomplete polymerization of the acrylate component, obtaining latex of acomplex rubber-like polymer of a polyorganosiloxane (L-1) with n-butylacrylate rubber.

[0120] The average particle size of the complex rubber-like polymer was120 nm, and the ratio of rubber-like polymers having a particle size of500 nm or more in 100% by weight of this complex rubber-like polymer(solid) was 0.1%. Further, the liquid temperature in the reactor loweredto 70° C., then, to this complex rubber latex was added an aqueoussolution composed of rongalite 0.25 parts ion exchanged water 10 parts,then, as the first stage, a mixture of acrylonitrile 2.5 parts styrene7.5 parts t-butyl hydroperoxide 0.05 parts was dropped over 2 hours, toeffect polymerization. After completion of dropping, condition of atemperature of 60° C. was kept for 1 hour, then, an aqueous solutioncomposed of ferrous sulfate hepta-hydrate 0.001 part disodiumethylenediamine tetraacetate 0.003 parts rongalite 0.2 parts Emal NC-35(manufactured by Kao Corp.) 0.2 parts ion exchanged water 10 parts wasadded, then, as the second stage, a mixture of acrylonitrile 10 partsstyrene 30 parts t-butyl hydroperoxide 0.2 parts was dropped over 2hours, to effect polymerization. After completion of dropping, conditionof a temperature of 60° C. was kept for 0.5 hours, then, cumenehydroperoxide 0.05 parts was added, further, a condition of atemperature of 60° C. was kept for 0.5 hours, then, the mixture wascooled to obtain graft copolymer latex obtained by graft- polymerizingacrylonitrile and styrene to a complex rubber-like polymer composed of apolyorganosiloxane (L-1) and butyl acrylate rubber.

[0121] Then, 150 parts of a 1% calcium acetate aqueous solution washeated to 60° C., and into this was gradually dropped 100 parts of thelatex of the graft copolymer, to cause coagulation. The precipitate wasdehydrated, washed, and dried to obtain a polyorganosiloxane/acrylatecomplex rubber-based graft copolymer (A-I-1).

Production Example 5 Production of Polyorganosiloxane/Acrylate ComplexRubber-Based Graft Copolymer (A-I-2)

[0122] Polymerization was conducted in the same manner as in ProductionExample 4 except that the mixture in the first step was changed toacrylonitrile 5 parts styrene 15 parts t-butyl hydroperoxide 0.1 part,and the mixture in the second step was changed to methyl methacrylate28.5 parts methyl acrylate 1.5 parts t-butyl hydroperoxide 0.15 parts,to give graft copolymer latex obtained by graft- polymerizingacrylonitrile and styrene in the first stage, and methyl methacrylateand methyl acrylate in the second stage, to a complex rubber-likepolymer composed of a polyorganosiloxane (L-1) and butyl acrylaterubber.

[0123] Then, coagulation, dehydration, washing and drying were conductedin the same manner as in Production Example 4, to obtain apolyorganosiloxane/acrylate complex rubber-like graft copolymer (A-I-2).

Production Example 6 Production of Polyorganosiloxane/Acrylate ComplexRubber-Based Graft Copolymer (A-I-3)

[0124] Into a reactor equipped with a reagent injection vessel, coolingtube, jacket heater and stirring apparatus was chargedpolyorganosiloxane latex (L-1) produced in 2 parts Production Example 1(solid content) Emal NC-35 (polyoxyethylene alkylphenyl ether 0.2 partssulfate; manufactured by Kao Corp.) ion exchanged water 148.5 parts, andthey were mixed, then, to this was added a mixture composed of n-butylacrylate 48 parts allyl methacrylate 1.08 parts 1,3-butylene glycoldimethacrylate 0.36 parts t-butyl hydroperoxide 0.11 parts.

[0125] The atmosphere was purged with nitrogen by passing a nitrogenflow through this reactor, the inner temperature was raised to 60° C.,and at this point, an aqueous solution composed of ferrous sulfatehepta-hydrate 0.000075 parts disodium ethylenediamine tetraacetate0.000225 parts rongalite 0.2 parts ion exchanged water 10 parts

[0126] was added, to initiate radical polymerization. By polymerizationof the acrylate component, the liquid temperature rose to 80° C. Thiscondition was maintained for 1 hour to complete polymerization of theacrylate component, obtaining latex of a complex rubber-like polymer ofa polyorganosiloxane (L-1) with n-butyl acrylate rubber.

[0127] The average particle size of the complex rubber-like polymer was145 nm, and the ratio of rubber-like polymers having a particle size of500 nm or more in 100% by weight of this complex rubber-like polymer(solid) was 0.3%.

[0128] Graft polymerization was conducted in the same manner as inProduction Example 4 excepting use of the resulted complex rubber,giving graft copolymer latex obtained by graft-polymerizingacrylonitrile and styrene to a complex rubber-like polymer composed of apolyorganosiloxane (L-1) and n-butyl acrylate rubber.

[0129] Then, coagulation, dehydration, washing and drying were conductedin the same manner as in Production Example 4, to obtain apolyorganosiloxane/acrylate complex rubber-like graft copolymer (A-I-3).

Production Example 7 Production of Polyorganosiloxane/Acrylate ComplexRubber-Based Graft Copolymer (A-I-4)

[0130] Into a reactor equipped with a reagent injection vessel, coolingtube, jacket heater and stirring apparatus was chargedpolyorganosiloxane latex (L-2) produced in 30 parts Production Example 2(solid content) ion exchanged water (including water in (L-2)) 295parts, and the reactor was purged with nitrogen, then, the reactionmixture was heated to 50° C., and to this was added a mixture composedof n-butyl acrylate 37.5 parts allyl methacrylate 2.5 parts t-butylhydroperoxide 0.3 parts, and the mixture was stirred for 30 minutes.Then, an aqueous solution composed of ferrous sulfate hepta-hydrate0.0003 parts disodium ethylenediamine tetraacetate 0.001 part rongalite0.17 parts ion exchanged water 5 parts

[0131] was added, to initiate radical polymerization. Thereafter, aninner temperature of 70° C. was maintained for 2 hours, to completepolymerization of the acrylate component, giving a complex rubber-likepolymer latex of a polyorganosiloxane (L-2) and n-butyl acrylate.

[0132] The average particle size of the complex rubber-like polymer was190 nm, and the ratio of rubber-like polymers having a particle size of500 nm or more in 100% by weight of this complex rubber-like polymer(solid) was 3%. Into this complex rubber latex was dropped a mixturecomposed of acrylonitrile 9 parts styrene 21 parts t-butyl hydroperoxide0.3 parts at an inner temperature of 70° C. over 45 minutes, then, atemperature of 70° C. was maintained for 4 hours, to complete graftpolymerization to the complex rubber-like polymer.

[0133] Then, this graft copolymer latex was added into a 12% calciumchloride aqueous solution of the same amount (liquid temperature: 60°C.) while stirring, then, a temperature of 80° C. was kept for 5minutes, further, a temperature of 95° C. was kept for 5 minutes, tocause coagulation. The precipitate was separated, washed, anddehydrated, then, dried at 85° C. for 24 hours, to obtain apolyorganosiloxane/acrylate complex rubber-like graft copolymer (A-I-4).

Production Example 8 Production of Polyorganosiloxane-Based GraftCopolymer (a-I-5)

[0134] Polymerization was conducted in the same manner as in ProductionExample 4 except that 50 parts (solid content) of the complexrubber-like polymer used was changed to 50 parts of a polyorganosiloxane(L-1, solid content), to give a graft copolymer (a-I-5) obtained bygrafting acrylonitrile and styrene to a polyorganosiloxane.

Production Example 9 Production of Diene-Based Graft Copolymer (a-I-6)

[0135] Into a reactor equipped with a reagent injection vessel, coolingtube, jacket heater and stirring apparatus was charged polybutadienelatex (average particle size: 50 parts 120 nm, ratio of particles havingparticle size of 500 nm or more: 0.2%) (solid content) at roomtemperature, and ion exchanged water (including water contained 140parts in rubber-like polymer latex) glucose 0.6 parts anhydrous sodiumpyrophosphate 0.01 part ferrous sulfate hepta-hydrate 0.005 parts sodiumhydroxide 0.1 part were added, the reactor was purged with nitrogenwhile the reaction mixture was stirred, then, the reaction mixture washeated to 50° C. Into this was dropped a mixture composed ofacrylonitrile 15 parts styrene 35 parts t-dodecylmercaptan 0.5 partscumene hydroperoxide 0.3 parts over 180 minutes while controlling sothat the inner temperature was not over 65° C. After completion ofdropping, cumene hydroperoxide 0.12 parts was added, further, themixture was maintained at the same temperature for 1 hour beforecooling. Then, to the resulted latex was added antioxidant (AntageW-400, manufactured by 1 part, Kawaguchi Kagaku Kogyo K.K.) and thelatex was added into a 1.2% sulfuric acid aqueous solution (liquidtemperature: 70° C.) of the same amount as this graft copolymer latex tocause coagulation, further, the temperature was raised to 90° C. andkept for 5 minutes, then, the product was dehydrated, washed and driedto obtain a diene-based graft copolymer (a-I-6) in the form ofopalescent powder.

Production Example 10 Production of Acrylate-Based Graft Copolymer(a-I-7)

[0136] Polymerization was conducted in the same manner as in ProductionExample 4 excepting that a polyorganosiloxane (L-1) was not used and theamount of n-butyl acrylate changed to 50 parts, giving a graft copolymer(a-I-7) obtained by grafting acrylonitrile and styrene to n-butylacrylate rubber.

[0137] The average particle size of the rubber-like polymer was 110 nm,and the ratio of particles having a particle size of 500 nm or more wasabout 0%.

Production Example 11 Production of Acrylate-Based Graft Copolymer(a-I-8)

[0138] To 10 parts of polybutadiene latex having a solid content of 35%(pH 10, gel content: 85%, average particle size: 80 nm, solid content)was added 0.2 parts (solid content) of an acid group-containingcopolymer latex having a solid content of 33% and an average particlesize of 80 nm composed of 81.5% of a n-butyl acrylate unit and 18.5% ofa methacrylic acid unit, and the mixture was stirred for 30 minutes,obtaining a thickened diene-based rubber-like polymer latex having anaverage particle size of 380 nm. To this was charged dipotassiumalkenylsuccinate 0.3 parts (Latemul ASK manufactured by Kao Corp., assubstantial amount, the same in the followings) ion exchanged water(including water in thickened 175 parts, butadiene-based polymer latex)and to this was added a mixture composed of n-butyl acrylate 40 parts,allyl methacrylate 0.16 parts, 1,3-butylene glycol dimethacrylate 0.08parts, t-butyl hydroperoxide 0.1 part while stirring. The atmosphere waspurged with nitrogen by passing a nitrogen flow through this reactor,the inner temperature was raised to 60° C. When the inner liquidtemperature reached 50° C., an aqueous solution composed of ferroussulfate hepta-hydrate 0.00015 parts disodium ethylenediaminetetraacetate 0.00045 parts rongalite 0.24 parts ion exchanged water 5.0parts was added, then, the inner temperature was raised to 75° C., toinitiate radical polymerization. This condition was maintained for 1hour to complete polymerization of the acrylate component, giving latexof a complex rubber- based rubber-like polymer of a thickenedbutadiene-based polymer with n-butyl acrylate rubber. The averageparticle size of this complex rubber-based rubber-like polymer latex was300 nm, and the ratio of particles having a particle size of 500 nm ormore was 51%. Then, an aqueous solution composed of rongalite 0.15 partsdipotassium alkenylsuccinate 0.65 parts ion exchanged water 10 parts wasadded, then, mixed liquid of acrylonitrile 6.3 parts styrene 18.7 partst-butyl hydroperoxide 0.11 parts was dropped over 1 hour, to causepolymerization. 5 minutes after completion of dropping, an aqueoussolution dissolving ferrous sulfate hepta-hydrate 0.001 part disodiumethylenediamine tetraacetate 0.003 parts rongalite 0.15 parts ionexchanged water 5 parts was added, then, mixed liquid of acrylonitrile6.3 parts styrene 18.7 parts t-butyl hydroperoxide 0.19 partsn-octylmercaptan 0.014 parts was dropped over 1 hour, to causepolymerization. After completion of dropping, a condition of atemperature of 75° C. was kept for 10 minutes, then, the mixture wascooled, and when the inner temperature was reached 60° C., a dispersioncomposed of antioxidant (Antage W-500, manufactured by 0.2 partsKawaguchi Kagaku Kogyo K.K.) dipotassium alkenylsuccinate 0.2 parts ionexchanged water 5 parts was added. The above-mentioned operation gavelatex of a graft copolymer obtained by graft-polymerizingacrylonitrile/styrene to a complex rubber-based rubber- like polymer ofa thickened butadiene-based polymer with n-butyl acrylate rubber.

[0139] Then, the above-mentioned polymer latex was added, whilestirring, into a 0.6% sulfuric acid aqueous solution heated to 45° C. ofan amount 1.2 fold of the whole latex, to coagulate a polymer. Then, theliquid temperature was raised to 65° C. and kept for 5 minutes, then,the liquid temperature was raised to 90° C. Then, the precipitate wasseparated, then, the recovered substance was added into water of 10-foldamount, then, stirred for 10 minutes, to effect washing treatment. Thisdispersion was dehydrated in a centrifugal dehydrator, further, dried at80° C. for 16 hours, to obtain a graft copolymer (a-I-8).

[0140] The average particle size and particle size distribution of thelatexes described in the production examples were all measured by usinga sub-micron particle size distribution measuring apparatus CHDF-2000manufactured by MATEC APPLIED SCIENCES.

Production Example 12 Production of Vinyl-Based (co)Polymer (B-1)

[0141] An acrylic resin (B-1) composed of 99 parts of methylmethacrylate and 1 part of methyl acrylate and showing a reducedviscosity measured at 25° C. from a N,N-dimethylformamide solution of0.25 dl/g was produced by known suspension polymerization.

Production Example 13 Production of Vinyl-Based (co)Polymer (B-2)

[0142] An acrylonitrile-styrene copolymer (B-2) composed of 29 parts ofacrylonitrile and 71 parts of styrene and showing a reduced viscositymeasured at 25° C. from a N,N-dimethylformamide solution of 0.60 dl/gwas produced by known suspension polymerization.

Production Example 14 Production of Vinyl-Based (co)Polymer (B-3)

[0143] An acrylonitrile-styrene-N-phenylmaleimide ternary copolymer(B-3) composed of 19 parts of acrylonitrile, 53 parts of styrene and 28parts of N-phenylmaleimide and showing a reduced viscosity measured at25° C. from a N,N-dimethylformamide solution of 0.65 dl/g was producedby known continuous solution polymerization.

Production Example 15 Production of Vinyl-Based (co)Polymer (B-4)

[0144] An acrylonitrile-amethylstyrene copolymer (B-4) composed of 25parts of acrylonitrile and 75 parts of a methylstyrene and showing areduced viscosity measured at 25° C. from a N,N-dimethylformamidesolution of 0.50 dl/g was produced by known continuous solutionpolymerization.

Examples 1 to 14 and Comparative Examples 1 to 5

[0145] The graft copolymers (A-I-1) to (A-I-4), (a-I-5) to (a-I-8)produced in the production examples, vinyl-based (co)polymers (B-1) to(B-4) produced in the production examples, polycarbonate (C-1,manufactured by Mitsubishi Enpla K.K., trade name: Eupiron S2000F),polyester (C-2, manufactured by Mitsubishi Rayon Co., Ltd., trade name:Tafpet N1300) were compounded in formulations shown in Tables 1 and 2(numerical values in the tables are by weight), further,ethylenebisstearylamide was added in an amount of 0.4 parts based on 100parts of these resin components, then, they were mixed using a Henschelmixer, and this mixture was fed to a deaerating type extruder (TEX-30manufactured by Nippon Seikosho K.K.) having a barrel temperature of230° C. or 260° C., and kneaded to obtain pellets.

[0146] Using the resulted pellets, the Izod impact strength, weatherresistance, brightness after direct vapor deposition, and hot platewelding property of the resin composition were measured and evaluated.The results are shown in Tables 1 and 2. Evaluations were conductedaccording to the following conditions.

[0147] (1) Izod Impact Strength

[0148] It was conducted by a method according to ASTM D256, and anotched Izod test piece having a thickness of ¼″ was left at 23° C. for12 hours or longer, then, the impact strength was measured.

[0149] (2) Weather Resistance

[0150] A white-colored plate of 100 mm×100 mm×3 mm was treated for 1000hours by Sunshine-weather-meter (manufactured by Suga Shikenki K.K.) ata black panel temperature of 63° C. and a cycle condition of 60 minutes(raining: 12 minutes). The weather resistance was evaluated by thedegree of discoloration (AE) measured by a color difference meter inthis case.

[0151] (3) Brightness after Direct Vapor Deposition

[0152] A plate of 100 mm×100 mm×3 mm was molded as a sample using aninjection molding machine manufactured by Toshiba Machine Co., Ltd.“IS80FP” under conditions of a cylinder set temperature of 230° C., amold temperature of 70° C. and an injection speed of 99%. Then, by avacuum vapor deposition method, an aluminum vapor deposited film havinga film thickness of about 50 nm was formed at a degree of vacuum of1×10⁻⁶ Torr, an electric current value of 400 mA and a film formationspeed of 1.5 mm/s. On this aluminum vapor deposited film, a top coatlayer of SiO₂ was vapor-deposited.

[0153] Regarding the molded article thus obtained by direct vapordeposition, the regular reflectance (%) and diffusion reflectance (%)were measured using a reflectometer (“HR-100” manufactured by MurakamiShikisai Gijutsu Kenkyusho), and brightness was evaluated.

[0154] (4) Hot Plate Welding Property

[0155] A hot plate processed with a fluorine resin was heated at asurface temperature of 300° C., a test sheet (30 mm×100 mm×3 mm) wasallowed to contact with this hot plate for 30 seconds, then, the testsheet was lifted vertically, and the stringing length in this operationwas measured, and the hot plate welding property was evaluated. When thestringing length is less than 1 mm, the evaluation was ⊚, when 1 mm ormore and less than 5 mm, the evaluation was , and when 5 mm or more,the evaluation was X.

[0156] (5) Falling Weight Impact Resistance

[0157] Using “Dupont impact tester” manufactured by Toyo SeikiSeisakusho, a weight of 1 kg was allowed to fall from a height of 1 mmon a sample plate of 100 mm×100 mm×3 mm under a punch diameter of{fraction (1/2)} inch and a cradle diameter of 3 inch, and crackedcondition of the sample plate was observed. No cracking was evaluated as, and cracking was evaluated as X. TABLE 1 Example Comparative Example1 2 3 1 2 3 4 Resin Graft copolymer (A) (A-I-1) 36 composition (A-I-2)36 (A-I-3) 36 (A-I-4) (a-I-5) 36 (a-I-6) 36 (a-I-7) 36 (a-I-8)Vinyl-based (co)polymer (B) (B-1) 29 29 29 29 29 29 100 (B-2) (B-3) 3535 35 35 35 35 (B-4) Content 1) (%) 18 18 18 18 18 18 0 Ratio 2) (mol %)0 0 0 0 — — — Average particle size 3) (nm) 120 120 145 50 120 110 —Ratio 4) (%) 0.1 0.1 0.3 0 0.2 0 — Material Izod impact strength [J/m]130 110 110 100 130 110 30 properties Weather resistance ΔE 3.0 2.1 3.02.6 10.6 3.3 0.5 Brightness 5) Regular 6) (%) 81.8 82.5 82.9 81.9 81.882.1 83.0 Diffuse 7) (%) 0.9 0.7 0.7 1.6 1.5 1.6 0.6 Hot plate weldingproperty ⊚ ⊚ ⊚ X ◯ X X Example 4 5 6 7 8 9 10 Resin Graft copolymer (A)(A-I-1) 36 36 36 27 24 32 80 composition (A-I-2) (A-I-3) (A-I-4) 9(a-I-5) (a-I-6) 12 (a-I-7) (a-I-8) 4 Vinyl-based (co)polymer (B) (B-1)64 22 30 26 29 20 (B-2) 29 (B-3) 35 35 35 35 (B-4) 42 Content 1) (%) 1818 18 20 18 18 40 Ratio 2) (mol %) 0 0 0 0.5 0 0 0 Average particle size3) (nm) 120 120 120 — — — 120 Ratio 4) (%) 0.1 0.1 0.1 1.0 0.1 5.8 0.1Material Izod impact strength [J/m] 120 160 110 140 130 140 480properties Weather resistance ΔE 2.2 4.1 3.8 3.0 6.3 3.4 2.6 Brightness5) Regular 6) (%) 82.0 81.9 81.7 82.0 81.8 81.6 82.6 Diffuse 7) (%) 0.80.9 0.9 1.3 0.9 1.3 1.1 Hot plate welding property ⊚ ⊚ ◯ ⊚ ◯ ⊚ ◯

[0158] TABLE 2 Example Comparative Example 11 12 13 Example5 14 ResinGraft copolymer (A) (A-I-1) 20 15 15 20 composition (A-I-4) 5 (a-I-6) 520 Vinyl-based (co)polymer (B) (B-2) 30 30 30 30 30 Polycarbonate (C-1)50 50 50 50 Polyester (C-2) 50 Content 1) (%) 10 11 10 10 10 Ratio 2)(mol %) 0 0.5 0 — 0 Average particle size 3) (nm) 120 — 120 120 120Ratio 4) (%) 0.1 1.0 0.1 0.2 0.1 Material Izod impact strength [J/m] 620610 610 580 210 properties Weather resistance ΔE 5.0 4.8 6.3 12.7 6.5Brightness 5) Regular 6) (%) 82.2 81.9 82.0 82.1 82.3 Diffuse 7) (%) 0.91.2 0.9 1.6 1.1 Hot plate welding property ⊚ ⊚ ⊚ ◯ ◯

[0159] The direct vapor depositing resin compositions of the presentinvention in Examples 1 to 14 had high Izod impact strength andexcellent weather resistance, and showed excellent brightness revealinglow diffusion reflectance after direct vapor deposition. Further, thestringing length in hot plate welding was short, and the hot platewelding property was also excellent.

[0160] On the other hand, the resin compositions in Comparative Examples1 to 5 were inferior in any one or more of the Izod impact resistance,weather resistance, and brightness after direct vapor deposition.

[0161] As shown from Examples 1 and 7, there was a tendency that whenthe ratio of silicon atoms having three or more siloxane bonds in apolyorganosiloxane contained in a graft copolymer (A-I) is higher, thediffusion reflectance after direct vapor deposition increases andbrightness deteriorates.

[0162] Particularly when the ratio of rubber having a particle size of500 nm or more in 100% by weight of the whole rubber-like polymer is 4%by weight or less as in Examples 1 to 8, 10 to 14, high Izod impactresistance, weather resistance and brightness after direct vapordeposition not known until now can be manifested.

Production Example 16 Production of Graft Copolymer (A-II-1)

[0163] Into a reactor equipped with a reagent injection vessel, coolingtube, jacket heater and stirring apparatus was charged ion exchangedwater 200 parts sodium carbonate 0.05 parts Phosphanol LO-529(polyoxylethylene alkylphenyl 0.3 parts ether phosphate; manufactured byToho Chemical Industry Co., Ltd.) rongalite 0.3 parts ferrous sulfatehepta-hydrate 0.000004 parts disodium ethylenediamine tetraacetate0.000012 parts, and the atmosphere was purged with nitrogen by passing anitrogen flow through this reactor while the reaction mixture wasstirred, the inner temperature was raised to 70° C., and mixed liquidcomposed of styrene 12 parts n-butyl acrylate 50 parts allylmethacrylate 0.6 parts t-butyl hydroperoxide 0.19 parts PhosphanolLO-529 0.8 was dropped over 3 hours, and after completion of dropping,the mixture was further kept for 2 hours to obtain a rubber-likepolymer. After that, an aqueous solution composed of rongalite 0.75parts ion exchanged water 5 parts was added, then, mixed liquid composedof methyl methacrylate 36 parts methyl acrylate 2 parts t-butylhydroperoxide 0.06 parts n-octylmercaptan 0.15 parts Phosphanol LO-5290.3 parts was dropped over 1.5 hours. Thereafter, the mixture was keptfor 30 minutes, to obtain graft copolymer latex. Then, 150 parts of a 1%calcium acetate aqueous solution was heated to 50° C., and into this wasdropped 100 parts of the latex of the graft copolymer gradually to causecoagulation. This slurry was further heated to 95° C. and kept for 5minutes, then, the precipitate was dehydrated, washed and dried, toobtain a graft copolymer (A-II-1) in the form of white powder.

Production Example 17 Production of Graft Copolymer (A-II-2)

[0164] Polyorganosiloxane latex (L-1) produced in 8 parts ProductionExample 1 (solid content) Emal NC-35 (polyoxyethylene alkylphenyl ether0.2 parts sulfate; manufactured by Kao Corp.) ion exchanged water 148.5parts, were added into a reactor equipped with a reagent injectionvessel, cooling tube, jacket heater and stirring apparatus, and mixed,then, to this was added a mixture composed of n-butyl acrylate 42 partsallyl methacrylate 0.3 parts 1,3-butylene glycol dimethacrylate 0.1 partt-butyl hydroperoxide 0.11 parts. The atmosphere was purged withnitrogen by passing a nitrogen flow through this reactor, the innertemperature was raised to 60° C., and at this point, an aqueous solutioncomposed of ferrous sulfate hepta-hydrate 0.000075 parts disodiumethylenediamine tetraacetate 0.000225 parts rongalite 0.2 parts ionexchanged water 10 parts was added, to initiate radical polymerization.By polymerization of the acrylate component, the liquid temperature roseto 78° C. This condition was maintained for 1 hour to completepolymerization of the acrylate component, obtaining latex of a complexrubber-like polymer of a polyorganosiloxane with n-butyl acrylaterubber. Further, the liquid temperature in the reactor lowered to 70°C., then, to this was added an aqueous solution composed of rongalite0.25 parts ion exchanged water 10 parts, then, as the first stage, amixture of methyl methacrylate 9.5 parts methyl acrylate 0.5 partst-butyl hydroperoxide 0.05 parts was dropped over 2 hours, to effectpolymerization. After completion of dropping, condition of a temperatureof 60° C. was kept for 1 hour, then, an aqueous solution composed offerrous sulfate hepta-hydrate 0.001 part disodium ethylenediaminetetraacetate 0.003 parts rongalite 0.2 parts Emal NC-35 (manufactured byKao Corp.) 0.2 parts ion exchanged water 10 parts was added, then, asthe second stage, a mixture of methyl methacrylate 38 parts methylacrylate 2 parts t-butyl hydroperoxide 0.2 parts was dropped over 2hours, to effect polymerization. After completion of dropping, conditionof a temperature of 60° C. was kept for 0.5 hours, then, cumenehydroperoxide 0.05 parts was added, further, a condition of atemperature of 60° C. was kept for 0.5 hours, then, the mixture wascooled to obtain graft copolymer latex obtained by graft- polymerizingmethyl methacrylate and methyl acrylate to a complex rubber-like polymercomposed of a polyorganosiloxane and butyl acrylate rubber.

[0165] Then, 150 parts of a 1% calcium acetate aqueous solution washeated to 60° C., and into this was gradually dropped 100 parts of thelatex of the graft copolymer, to cause coagulation. The precipitate wasdehydrated, washed, and dried to obtain a graft copolymer (A-II-2).

Production Example 18 Production of Graft Copolymer (A-II-3)

[0166] Into a reactor equipped with a reagent injection vessel, coolingtube, jacket heater and stirring apparatus was charged ferric sulfatehepta-hydrate 0.00004 parts disodium ethylenediamine tetraacetate0.00012 parts rongalite 0.2 parts ion exchanged water 190 parts and themixture was heated to 80° C. while stirring under a nitrogen flow. Tothis was added {fraction (1/10)} of a mixture composed of methylmethacrylate 12.1 parts methyl acrylate 10.9 parts styrene 1.1 partsethylene glycol dimethacrylate 0.8 parts allyl methacrylate 0.1 partt-butyl hydroperoxide 0.1 part Phosphanol LO-529 0.8 parts and kept for15 minutes, then, remaining {fraction (9/10)} of the mixture was droppedover 3 hours to cause polymerization, then, the reaction mixture waskept for 1 hour at 80° C. without change, to effect polymerization ofthe innermost layer (core part). Then, to this core part latex was addedan aqueous solution composed of 0.2 parts of rongalite and 5 parts ofion exchanged water, further, a mixture composed of n-butyl acrylate30.6 parts styrene 6.3 parts ethylene glycol dimethacrylate 0.1 partdiallyl malate 0.5 parts t-butyl hydroperoxide 0.12 parts PhosphanolLO-529 0.7 parts was dropped over 3 hours to cause polymerization, then,the reaction mixture was further kept for 2 hours at 80° C. withoutchange, to effect polymerization of the intermediate layer (rubberpart). Then, in the presence of this latex, an aqueous solution composedof 0.12 parts of rongalite and 5 parts of ion exchanged water was added,then, a mixture composed of methyl methacrylate 35.5 parts methylacrylate 2.0 parts t-dodecylmercaptan 0.2 parts t-butyl hydroperoxide0.1 part was dropped over 2 hours to cause polymerization, then, thereaction mixture was further kept for 1 hour at 80° C. without change,to effect polymerization of the outermost layer (graft part), obtaininglatex of a graft copolymer (A-II-3) having a three-layer structure.

[0167] This latex was coagulated and recovered in the same manner as forthe graft copolymer (A-II-1) in Production Example 16, to obtain a graftcopolymer (A-II-3) which is a white powder.

Production Example 19 Production of Graft Copolymer (A-II-4)

[0168] Into a reactor equipped with a reagent injection vessel, coolingtube, jacket heater and stirring apparatus was added polyorganosiloxanelatex (L-3) (solid content) 8 parts Emal NC-35 (polyoxyethylenealkylphenyl ether 0.2 parts sulfate; manufactured by Kao Corp.) ionexchanged water 148.5 parts, and these were mixed, then, a mixturecomposed of n-butyl acrylate 42 parts allyl methacrylate 0.3 parts1,3-butylene glycol dimethacrylate 0.1 part t-butyl hydroperoxide 0.11parts was added. The atmosphere was purged with nitrogen by passing anitrogen flow through this reactor, the inner temperature was raised to60° C., and at this point, an aqueous solution composed of ferroussulfate hepta-hydrate 0.000075 parts disodium ethylenediaminetetraacetate 0.000225 parts rongalite 0.2 parts ion exchanged water 10parts was added, to initiate radical polymerization. By polymerizationof the acrylate component, the liquid temperature rose to 78° C. Thiscondition was maintained for 1 hour to complete polymerization of theacrylate component, obtaining latex of a complex rubber-like polymer ofa polyorganosiloxane with n-butyl acrylate rubber. Further, the liquidtemperature in the reactor lowered to 70° C., then, to this was added anaqueous solution composed of rongalite 0.25 parts ion exchanged water 10parts, then, as the first stage, a mixture of methyl methacrylate 9.5parts methyl acrylate 0.5 parts t-butyl hydroperoxide 0.05 parts wasdropped over 2 hours, to effect polymerization. After completion ofdropping, condition of a temperature of 60° C. was kept for 1 hour,then, an aqueous solution composed of ferrous sulfate hepta-hydrate0.001 part disodium ethylenediamine tetraacetate 0.003 parts rongalite0.2 parts Emal NC-35 (manufactured by Kao Corp.) 0.2 parts ion exchangedwater 10 parts was added, then, as the second stage, a mixture of methylmethacrylate 38 parts methyl acrylate 2 parts t-butyl hydroperoxide 0.2parts was dropped over 2 hours, to effect polymerization. Aftercompletion of dropping, condition of a temperature of 60° C. was keptfor 0.5 hours, then, cumene hydroperoxide 0.05 parts was added, further,a condition of a temperature of 60° C. was kept for 0.5 hours, then, themixture was cooled to obtain graft copolymer latex obtained by graft-polymerizing methyl methacrylate and methyl acrylate to a complexrubber-like polymer composed of a polyorganosiloxane and butyl acrylaterubber.

[0169] Then, 150 parts of a 1% calcium acetate aqueous solution washeated to 60° C., and into this was gradually dropped 100 parts of thelatex of the graft copolymer, to cause coagulation. The precipitate wasdehydrated, washed, and dried to obtain a graft copolymer (A-II-4).

Production Example 20 Production of Graft Copolymer (a-II-5)

[0170] Into a reactor equipped with a reagent injection vessel, coolingtube, jacket heater and stirring apparatus was charged polybutadienelatex (average particle size: 50 parts 290 nm) (solid content) at roomtemperature, and to this was added ion exchanged water (including watercontained 140 parts in rubber-like polymer latex) glucose 0.6 partsanhydrous sodium pyrophosphate 0.01 part ferrous sulfate hepta-hydrate0.005 parts sodium hydroxide 0.1 part and the atmosphere was purged withnitrogen while the reaction mixture was stirred, then the reactionmixture was raised to 50° C., into this was dropped a mixture composedof acrylonitrile 15 parts styrene 35 parts t-dodecylmercaptan 0.5 partscumene hydroperoxide 0.3 parts over 180 minutes, and controlled so thatthe inner temperature was not over 65° C. After completion of dropping,cumene hydroperoxide 0.12 parts was added, further, the reaction mixturewas kept for 1 hour before cooling. Then, to the resulted latex wasadded antioxidant (Antage W-400, manufactured by 1 part, KawaguchiKagaku Kogyo K.K.) and the latex was added into a 1.2% sulfuric acidaqueous solution (liquid temperature: 70° C.) of the same amount as thisgraft copolymer latex to cause coagulation, further, the temperature wasraised to 90° C. and kept for 5 minutes, then, the product wasdehydrated, washed and dried to obtain a graft copolymer (a-II-5) in theform of opalescent powder.

Production Example 21 Production of Graft Copolymer (a-II-6)

[0171] Polymerization was conducted in the same manner as in ProductionExample 17 excepting that methyl methacrylate and methyl acrylate usedin the first stage were changed to 2.5 parts of acrylonitrile and 7.5parts of styrene, and methyl methacrylate and methyl acrylate used inthe second stage were changed to 10 parts of acrylonitrile and 30 partsof styrene, obtaining graft copolymer latex obtained bygraft-polymerizing acrylonitrile and styrene to a complex rubber-likepolymer composed of a polyorganosiloxane and butyl acrylate rubber.

[0172] Then, coagulation, dehydration, washing and drying were conductedin the same manner as in Production Example 17 to obtain a graftcopolymer (a-II-6).

Production Example 22 Production of Graft Copolymer (a-II-7)

[0173] Into a stainless autoclave equipped with a reagent injectionvessel, water cooling jacket heater and stirring apparatus was chargedion exchanged water 190 parts n-butyl acrylate 50 parts beef fattypotassium 1 part sodium N-lauroylsarcosinate 0.5 partsdiisopropylbenzene hydroperoxide 0.2 parts anhydrous sodium sulfate 0.2parts and the atmosphere was purged with nitrogen while the reactionmixture was stirred. Further, 1,3-butadiene 50 parts was charged, andthe inner temperature was raised to 40° C. Then, a mixture composed ofion exchanged water 10 parts dextrose 0.2 parts rongalite 0.05 partsanhydrous sodium pyrophosphate 0.2 parts disodium ethylenediaminetetraacetate 0.001 part ferrous sulfate hepta-hydrate 0.003 parts wasadded, to cause polymerization. The inner temperature was raised to 50°C. by polymerization heat generation and temperature rising, and thejacket was controlled so that the temperature was constant at thistemperature, finally, polymerization was completed in 9 hours, obtaininga rubber-like polymer having an average particle size of 105 nm. Then,into a reactor equipped with a cooling tube, jacket heater and stirringapparatus was charged the following components under nitrogen flow, andthe mixture was heated to an inner temperature of 65° C. while stirring.potassium oleate 2.2 parts sodium dioctylsulfosuccinate (70% solution)3.6 parts sodium formaldehyde sulfoxylate di-hydrate 0.3 parts ferroussulfate hepta-hydrate 0.003 parts disodium ethylenediamine tetraacetate0.009 parts ion exchanged water 200 parts. To this was added a mixturecomposed of n-butyl acrylate 81.5 parts methacrylic acid 18.5 partscumene hydroperoxide 0.5 parts over 2 hours, and also after completionof addition, polymerization was continued at the same temperature for 2hours, to obtain an acid group-containing copolymer latex for thickeninghaving an average particle size of 150 nm. 70 parts (solid content) ofthe resulted rubber- like polymer latex was charged into a reactorequipped with a cooling tube, jacket heater and stirring apparatus, thecontent was stirred at room temperature, and pH was controlled to 9.2with a 2% sodium carbonate aqueous solution. Further, 1.2 parts of theacid group- containing copolymer latex (solid content) was charged,stirring was continued for 30 minutes for thickening treatment,obtaining thickened rubber-like polymer latex having an average particlesize of 190 nm. Further, while continuing stirring, ion exchanged water(also including water in 200 parts rubber-like polymer latex) rongalite0.14 parts sodium N-lauroylsarcosinate 0.35 parts were added, the innertemperature was raised to 75° C., and a mixture of the followingcompounds was continuously added over 90 minutes, for polymerization.methyl methacrylate 28.8 parts ethyl acrylate 1.2 parts n-ocrylmercaptan0.05 parts cumene hydroperoxide 0.12 parts.

[0174] After completion of addition, the inner temperature was kept atthis temperature further for 60 minutes, completing polymerization.

[0175] To the resulted graft copolymer latex was added 0.4 parts ofstyrenated phenol, 0.3 parts of dilauryl thiopropionate and 0.4 parts oftriphenyl phosphite, then, a 0.25% dilute sulfuric acid aqueous solutionheated to 50° C. of an amount 2-fold of the graft latex was added toprecipitate a graft copolymer, further, thermally treated at 90° C. for5 minutes, then, washed with water, and dehydration thereof was repeatedseveral times, and finally dried to obtain a graft copolymer (a-II-7)which is a white powder.

Production Example 23 Production of Graft Copolymer (a-II-8)

[0176] Polymerization was conducted in the same manner as in ProductionExample 16 excepting that 36 parts of methyl methacrylate and 2 parts ofmethyl acrylate used in graft polymerization was changed to 10 parts ofacrylonitrile and 28 parts of styrene, obtaining graft copolymer latexobtained by graft-polymerizing acrylonitrile and styrene to butylacrylate rubber.

[0177] Then, coagulation, dehydration, washing and drying were conductedin the same manner as in Production Example 16 to obtain a graftcopolymer (a-II-8).

Examples 15 to 27 and Comparative Examples 6 to 11

[0178] The graft copolymers (A-II-1) to (A-II-4), (a-II-5) to (a-II-8),(a-I-8) produced in the production examples, polymers (B-1) to (B-4)produced in the production examples, polycarbonate (C-1, manufactured byMitsubishi Enpla K.K., trade name: Eupiron S2000F), polyester (C-2,manufactured by Mitsubishi Rayon Co., Ltd., trade name: Tafpet N1300)were compounded in formulations shown in Tables 3 and 4 (numericalvalues in the tables are by weight), further, ethylenebisstearylamidewas added in an amount of 0.4 parts based on 100 parts of these resincomponents, then, they were mixed using a Henschel mixer, and thismixture was fed to a deaerating type extruder (TEX-30 manufactured byNippon Seikosho K.K.) having a barrel temperature of 230° C. or 260° C.,and kneaded to obtain pellets.

[0179] Using the resulted pellets, the Izod impact strength, weatherresistance, brightness after direct vapor deposition, and hot platewelding property of the resin composition were measured and evaluated asdescribed above. The results are shown in Tables 3 and 4. TABLE 3Example Comparative Example 15 16 17 6 7 8 9 Resin Graft copolymer (A)(A-II-1) 29 composition (A-II-2) (A-II-3) 40 (A-II-4) 36 (a-II-5) 36(a-II-6) (a-II-7) 26 (a-II-8) 29 (a-I-8) Vinyl-based (co)polymer (B)(B-1) 100 (B-2) 71 60 64 64 71 74 (B-3) (B-4) Ratio 8) 0 0 0 100 0 50 0Ratio 9) 100 100 100 0 0 100 — Material Falling weight impact strength ◯◯ ◯ ◯ ◯ ◯ X properties Weather resistance ΔE 3.0 3.1 2.8 12.3 3.7 5.60.5 Brightness 5) Regular 6) (%) 82.6 82.6 82.8 82.3 81.4 81.9 83.0Diffuse 7) (%) 1.0 1.2 1.3 1.6 1.9 1.8 0.8 Hot plate welding property ⊚⊚ ⊚ ◯ ◯ X X Example 18 19 20 21 22 23 24 Resin Graft copolymer (A)(A-II-1) 29 29 29 23 23 23 composition (A-II-2) 36 (A-II-3) (A-II-4)(a-II-5) 8 (a-II-6) 8 (a-II-7) (a-II-8) (a-I-8) 8 Vinyl-based(co)polymer (B) (B-1) 36 (B-2) 35 39 32 69 69 69 64 (B-3) 32 (B-4) 39Ratio 8) 0 0 0 22 0 9 0 Ratio 9) 100 100 100 70 70 70 100 MaterialFalling weight impact strength ◯ ◯ ◯ ◯ ◯ ◯ ◯ properties Weatherresistance ΔE 2.6 3.2 3.0 3.4 3.1 3.6 2.8 Brightness 5) Regular 6) (%)82.1 81.9 82.1 81.5 82.3 81.7 82.8 Diffuse 7) (%) 0.9 1.1 1.0 1.1 1.11.3 1.0 Hot plate welding property ⊚ ⊚ ◯ ◯ ⊚ ◯ ⊚

[0180] TABLE 4 Comparative Example Example Example 25 26 10 11 27 ResinGraft copolymer (A) (A-II-1) 20 15 20 composition (a-II-5) 5 25 (a-II-7)18 Vinyl-based (co)polymer (B) (B-2) 30 30 25 32 30 Polycarbonate (C)(C-1) 50 50 50 50 Polyester (C) (C-2) 50 Ratio 8) 0 21 100 50 0 Ratio 9)100 70 0 100 100 Material Falling weight impact strength ◯ ◯ ◯ ◯ ◯properties Weather resistance ΔE 3.9 4.2 13.2 8.2 4.5 Brightness 5)Regular 6) (%) 82.3 81.9 81.6 81.9 82.0 Diffuse 7) (%) 1.1 1.2 1.6 1.71.2 Hot plate welding property ⊚ ⊚ ◯ X ◯

[0181] The resin compositions of the present invention in Examples 15 to27 had excellent weather resistance, and showed excellent brightnessrevealing low diffusion reflectance after direct vapor deposition.Further, the stringing length in hot plate welding was short, and thehot plate welding property was also excellent.

[0182] On the other hand, the resin compositions in Comparative Examples6 to 11 were inferior in any one or more of the weather resistance,brightness after direct vapor deposition and hot plate welding property.

[0183] As shown in Examples 15 to 27, the ratio of methyl methacrylatein the grafted part composition (100% by weight) of a graft copolymercontained in the resin composition is preferably from 70 to 100% byweight.

INDUSTRIAL APPLICABILITY

[0184] According to the present invention, a direct vapor depositingresin composition capable of providing a beautiful bright appearanceafter direct vapor deposition of a metal, further, having high levelmechanical strengths such as impact strength and the like, and weatherresistance, and also excellent in hot plate welding property with atransparent resin such as PMMA resins, polycarbonate resins and thelike, and a molded article obtained by using this resin composition, canbe provided.

[0185] Particularly, balance of weather resistance, brightness afterdirect vapor deposition and hot plate welding property is extremelyexcellent as compared with conventionally known rubber-modified resincompositions, and the direct vapor depositing resin composition of thepresent invention provides an extremely high utility value as variousindustrial materials.

What is claimed is:
 1. A direct vapor depositing resin compositioncomprising at least one selected from the group consisting of thefollowing graft copolymers (A-I) and (A-II). (A-I): A graft copolymerobtained by graft-polymerizing one or more monomers or a monomer mixtureto a complex rubber-like polymer (G) composed of a polyorganosiloxaneand a (meth)acrylate-based polymer. (A-II): A graft copolymer obtainedby graft-polymerizing one or more monomers or a monomer mixtureincluding an alkyl(meth)acrylate as an essential component to arubber-like polymer (R) in which the content of diene units is 30% byweight or less (including 0% by weight) in 100% by weight of the wholerubber-like polymer.
 2. The direct vapor depositing resin compositionaccording to claim 1 wherein the composition comprises a vinyl-based(co)polymer (B) having as a constituent unit at least one selected fromthe group consisting of aromatic alkenyl units, vinyl cyanide units andalkyl (meth)acrylate units.
 3. The direct vapor depositing resincomposition according to claim 2 wherein the total content of said graftcopolymers (A-I) and (A-II) is from 5 to 95% by weight based on thetotal amount of the graft copolymers (A-I) and (A-II) and thevinyl-based (co)polymer (B), and the content of the vinyl-based(co)polymer (B) is from 95 to 5% by weight based on the total amount ofthe graft copolymers (A-I) and (A-II) and the vinyl-based (co)polymer(B).
 4. The direct vapor depositing resin composition according to anyof claims 1 to 3 wherein the composition comprises a polycarbonateand/or polyester (C).
 5. The direct vapor depositing resin compositionaccording to claim 4 wherein the total content of said graft copolymers(A-I) and (A-II) is from 5 to 80% by weight based on the total amount ofthe graft copolymers (A-I) and (A-II), vinyl-based (co)polymer (B) andpolycarbonate and/or polyester (C), the content of said vinyl-based(co)polymer (B) is from 75 to 0% by weight based on the total amount ofthe graft copolymers (A-I) and (A-II), vinyl-based (co)polymer (B) andpolycarbonate and/or polyester (C), and the content of saidpolycarbonate and/or polyester (C) is from 95 to 20% by weight based onthe total amount of the graft copolymers (A-I) and (A-II), vinyl-based(co)polymer (B) and polycarbonate and/or polyester (C).
 6. The directvapor depositing resin composition according to any of claims 1 to 5wherein the composition comprises said graft copolymer (A-I) and, inthis graft copolymer (A-I), the ratio of rubber-like polymers having aparticle size of 500 nm or more is less than 4% by weight, in allrubber-like polymers including a complex rubber-like polymer (G).
 7. Thedirect vapor depositing resin composition according to any of claims 1to 6 wherein the composition comprises said graft copolymer (A-I) and,in this graft copolymer (A-I), the content of a polyorganosiloxane in acomplex rubber-like polymer (G) is from 1 to 99% by weight based on thetotal amount of a polyorganosiloxane and a (meth)acrylate-based polymer.8. The direct vapor depositing resin composition according to any ofclaims 1 to 7 wherein the composition comprises said graft copolymer(A-I) and this graft copolymer (A-I) is a graft copolymer obtained bygraft-polymerizing one or more monomers or a monomer mixture to acomplex rubber-like polymer (G) composed of a (meth)acrylate-basedpolymer and a polyorganosiloxane in which the content of silicon atomshaving three or more siloxane bonds is 1 mol % or less (including 0 mol%) based on all silicon atoms in polydimethylsiloxane.
 9. The directvapor depositing resin composition according to any of claims 1 to 8wherein the composition comprises said graft copolymer (A-II) and, inthis graft copolymer (A-II), the rubber-like polymer (R) contains as aconstituent unit at least one of alkyl acrylate units having an alkylgroup containing 2 to 8 carbon atoms.
 10. The direct vapor depositingresin composition according to any of claims 1 to 8 wherein thecomposition comprises said graft copolymer (A-II) and, in this graftcopolymer (A-II), said one or more monomers or a monomer mixturecontaining an alkyl(meth)acrylate as an essential component to begraft-polymerized to the rubber-like polymer (R) contains analkyl(meth)acrylate in an amount of 50 to 100% by weight.
 11. A moldedarticle obtained by molding the direct vapor depositing resincomposition according to any of claims 1 to
 10. 12. A molded articleaccording to claim 11 wherein its surface is metallized by direct vapordeposition.
 13. A lamp housing obtained by metallization by direct vapordeposition of the surface of a molded article obtained by molding thedirect vapor depositing resin composition according to any of claims 1to 10.